点击化学制备毛细管整体柱及其应用

发布时间：2018-04-29 20:20

本文选题：整体柱 + 点击化学　；参考：《西北大学》2017年硕士论文

【摘要】：整体柱是一种具有广阔应用前景的新型色谱固定相,也是目前液相色谱领域研究的一个热点。基于巯基的绿色点击化学反应,具有反应条件温和、产率高等特点,目前已经被广泛应用于聚合物的制备以及材料表面修饰等方面。然而,目前鲜有文献报道点击化学反应直接制备整体柱的研究。本论文针对目前有机整体柱和杂化整体柱中存在的一些问题,本文发展了三种基于点击反应制备整体柱的新技术:1.针对整体柱制备周期长的问题,采用巯基-丙烯酸酯(thiol-acrylate)点击聚合反应快速制备有机整体柱。十八硫醇的引入有效地抑制传统自由基聚合过程中的氧阻聚现象。此反应过程中既包含丙烯酸酯间的自聚反应,又存在丙烯酸酯与巯基间的共聚反应。所制备的有机整体柱对苯系物实现高效分离,最高柱效达75,000 N/m。对四种标准混合蛋白酶解液的分离效果与C-18填充柱结果相当。并且结合液质联用(cLC-MS)技术首次将毛细管整体柱应用于长柄扁桃蛋白质的分离鉴定。2.针对整体柱表面性质较难调控的问题,采用“两步”巯基-烯(thiol-ene)点击聚合反应制备了一种多孔亲水性杂化整体柱。通过与1-硫代甘油反应,疏水性单体八乙烯基倍半硅烷在致孔剂中的溶解性得到了显著提高,然后将其作为前驱体成功制备了杂化整体柱。所制备的杂化整体柱具有连续均匀的网状结构,在cLC应用中显示出典型的HILIC保留机理,最高柱效达65,000 N/m。此外,本研究将肼功能化后的杂化整体材料成功应用于糖肽的富集。3.针对有机聚合物整体柱分离柱效低的问题,首次使用巯基-马来酰亚胺(thiol-maleimide)点击聚合反应直接合成两种高交联的有机聚合物整体柱。所制备的有机整体柱具有良好的热稳定性和机械强度。在5分钟内实现对苯系物的高效分离,最高柱效可达180,500 N/m。此外,对苯酚类、碱性化合物、EPA 610、HeLa酶解液等样品均展现出令人满意的分离效果,为提高有机整体柱对小分子化合物分离柱效提供了一种新思路。
[Abstract]:Monolithic column is a new chromatographic stationary phase with broad application prospect, and it is also a hot spot in the field of liquid chromatography. The green click chemical reaction based on sulfhydryl group has been widely used in the preparation of polymers and the surface modification of materials because of its mild reaction conditions and high yield. However, there are few reports on the direct preparation of monolithic columns by clicking on chemical reactions. Aiming at some problems existing in organic monolithic column and hybrid monolithic column, this paper develops three new techniques for preparing monolithic column based on click-reaction: 1. In order to solve the problem of long preparation period of monolithic column, the organic monolithic column was rapidly prepared by mercapto-acrylic acid thiol-acrylate click-polymerization reaction. The introduction of octadecyl mercaptan can effectively inhibit the phenomenon of oxygen inhibition in the process of traditional free radical polymerization. The reaction includes both the self-polymerization of acrylate and the copolymerization of acrylic ester and sulfhydryl group. The organic monolithic column was used to separate benzene series with the highest column efficiency of 75000 N / m. The separation effect of four standard mixed proteolytic solutions was similar to that of C-18 packed column. The capillary monolithic column was applied to the separation and identification of almond protein for the first time. A porous hydrophilic hybrid monolithic column was prepared by "two-step" mercapto thiol-ene click-polymerization to solve the problem that it is difficult to control the surface properties of monolithic column. The solubility of hydrophobic monomer octavinyldisilane in pore-forming agent was significantly improved by reaction with 1-thioglycerol, and then the hybrid monolithic column was successfully prepared as a precursor. The hybrid monolithic column has a continuous and uniform reticular structure, which shows typical HILIC retention mechanism in the application of cLC. The maximum column efficiency is 65000 N / m. In addition, the hybrid monolithic material of hydrazine functionalized was successfully applied to the enrichment of glycopeptide. 3. In order to solve the problem of low column separation efficiency, two highly crosslinked organic polymer monolithic columns were synthesized by using mercapto-maleimide one-click polymerization for the first time. The prepared organic monolithic column has good thermal stability and mechanical strength. The highest column efficiency of 180500 N / m was achieved in 5 minutes. In addition, samples such as phenol, alkaline compound EPA 610N HeLa hydrolysate showed satisfactory separation effect, which provided a new way to improve the column efficiency of organic monolithic column for the separation of small molecular compounds.
【学位授予单位】：西北大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O652.6

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